Method of controlling pests with thioureido carbamates compounds

ABSTRACT

WHEREIN R can be selected from lower alkyl, lower haloalkyl, phenyl, substituted phenyl wherein said substituents can be selected from halogen and lower alkyl; R1 can be selected from lower alkyl, lower alkoxy and lower thioalkyl. The compounds are useful fungicides and biocides.   New compounds corresponding to the generic formula:

1m 3,927,219 1 Dec, 16, 1975 METHOD OF CONTROLLING PESTS WITH THIOUREIDO CARBAMATES COMPOUNDS [75] Inventor: Alexander Mihailovski, Berkeley,

Calif.

[73] Assignee: Stauffer Chemical Company,

Westport, Conn.

[22] Filed: June 12, 1974 [21] Appl. No.: 478,485

Related US. Application Data [62] Division of Ser. No. 217,697, Dec. 29, 1971, Pat. No.

[52] US. Cl. 424/300; 424/46; 424/168; 424/357 [51] Int. Cl. A01N 9/12 [58] Field of Search 424/300, 321

[56] References Cited UNITED STATES PATENTS 3,776,936 12/1973 Singhal et a1. 424/300 3,781,330 12/1973 Nikles 424/300 3,832,384 8/1974 Mihailovski 424/321 Primary ExaminerSam Rosen Assistant Examiner-Dale Rv Ore Attorney, Agent, or FirmDaniel C. Block [57] ABSTRACT New compounds corresponding to the generic formula:

29 Claims, NO Drawings METHOD OF CONTROLLING PESTS WITH THIOUREIDO CARBAMATES COMPOUNDS This is a division of application Ser. No. 217,697. filed Dec. 29, 1971, now US. Pat. No. 3.832.384.

DESCRIPTION OF THE INVENTION This invention is directed to a novel group of compounds which may be generally described as thioureido sulfonanilides which are highly active fungicides and biocides. The compounds of the present invention are represented by the generic formula:

wherein R can be selected from lower alkyl, lower haloalkyl, phenyl, substituted phenyl wherein said substituents can be selected from halogen and lower alkyl; R can be selected from lower alkyl, lower alkoxy and lower thioalkyl.

The above compounds can be prepared by treating a Z-aminoalkylsulfonanilide or Z-aminoarylsulfonanilide with an appropriate carbonyl isothiocyanate in an inert solvent such as acetone or the like. The products form rapidly and can be isolated in good purity.

In order to illustrate the merits of the present invention the following examples are provided.

EXAMPLE 1 Preparation of 2-[ 3 Ethoxycarbonyl )-thioureido ]-benzenesulfonanilide To 5.0 g. (0.020 mole) of 2-aminobenzenesulfonanilide dissolved in 30 ml. of acetone were added with stirring 2.6 (0.020 mole) ethoxycarbonyl isothiocyanate dissolved in ml. of acetone. This mixture was stirred for 16 hours at room temperature and the precipitated solid was filtered to yield 6.3 g. of 2-[3'- ethoxycarbonyl)-thioureido]-benzenesulfonanilide, mp. l80l8lC. (dec.). Yield, 83% of theory.

EXAMPLE 2 Preparation of 2- 3 Ethoxycarbonyl -thioureido -methanesulfonanilide To 5.0 g. 0.027 mole) 2-amin0methanesulfonanilide dissolved in 20 ml. of acetone were added 3.5 g. (0.027 mole) ethoxycarbonyl isothiocyanate dissolved in 10 ml. of acetone. A colorless solid precipitated which was filtered to give 7.4 g. of 2-[3-(ethoxycarbonyl)-thioureido]-methanesulfonanilide, m.p. l68l69C. (dec.). Yield, 87% of theory.

Other compounds were prepared in an analogous manner starting with the appropriate starting materials as outlined above. The following is a table of compounds representative of those embodied by the present invention. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

TABLE l-continued FUNGICIDE TESTING PROCEDURES A. Foliar Preventative Sprays 1. Bean Rust The chemicals are dissolved in an appropriate solvent and diluted with water containing several drops of Tween 20. a wetting agent. Test concentrations, ranging from 1000 ppm downward. are sprayed to runoff on the primary leaves of pinto beans (Phaseolus vulgaris L. After the leaves are dried. they are inoculated with a water suspension of spores of the bean rust fungus Uromyces p/zaseoli Arthur) and the plants are placed in an environment of 100% humidity for 24 hours. The plants are then removed from the humidity chamber and held until disease pustules appear on the leaves. Efi'ectiveness is recorded as the lowest concentration, in ppm which will provide 50% reduction in pustule formation as compared to untreated inoculated plants.

removed from the humidity chamber and held until disease lesions appear on the leaves. Effectiveness is recorded as the lowest concentration, in ppm, which will provide 50% reduction in number of lesions formed as compared to untreated inoculated plants.

-B. Tube Systemic Test 1. Bean Rust The chemicals are dissolved in an appropriate solvent and diluted with tap water to a series of descending concentrations beginning at 50 ppm. Sixty ml. of each concentration are placed in a test tube. A pinto bean plant is placed in each tube and supported with a piece of cotton so that only the roots and lower stem are in contact with the test solution. Forty-eight hours later the bean leaves are inoculated with a water suspension of spores of the bean rust fungus and placed in an environment with 100% humidity for 24 hours. The plants are then removed from the humidity chamber and maintained in the greenhouse until the disease pustules appear on the leaves. Effectiveness is recorded as the lowest concentration, in ppm, which will provide 50% reduction in pustule formation as compared to untreated, inoculated plants.

2. Bean Powdery Mildew Test chemicals are prepared and applied in the same manner as for the bean rust systemic test. After two days the leaves are dusted with spores of the powdery mildew fungus and maintained in the greenhouse until mycelial growth appears on the leaf surfaces. Effectiveness is recorded as the lowest concentration, in ppm, which will provide a 50% reduction in mycelial growth on the leaf surface as compared to untreated, inoculated plants. C. Systemic Soil Drench 1. Bean Rust Pinto beans are grown in l-pint ice cream cartons, each containing 1 lb. of soil. Aliquots of the toxicant, dissolved in an appropriate solvent, are diluted with 25 ml. of water and drenched onto the soil surface. Two

Beah pewdety Mlldew days later the bean leaves are inoculated with a water Test ehethleats are P p and PP 1h the Same suspension of spores of the rust fungus, and the plants manner as for the bean rust test. After the plants are are placed in an environment with 00% humidity for y the leaves are dhsted with Pe of the Powdery 24 hours. The plants are then removed from the humidmlldew fungus (QY Ph P 58 De cahdehe) ahd ity chamber and maintained in the greenhouse until the the plants are retalhed the greenhouse l the h' pustules appear on the leaves. Etfectiveness is recorded gal growth pp on the leaf surface htfeettvehese as the minimum concentration, in ppm per lb. of soil, reeotdedes the lowest eeheehtratleht pp Wh1eh which will provide reduction in number of pus- Wlh Provide 50% redhehoh P feh'hatleh as tules as compared to untreated inoculated plants. compared to untreated inoculated plants. 2 Bean powdery Mildew y Bhght 50 The bean plants and chemicals are prepared and Test chemlcals are P p and pp P the Same applied as in the rust systemic soil drench test. After 10 mahher as the beah rust and P y hhldew tests days, the bean leaves are dusted with spores of the except 4Week Old tomato (L C()persic0n eSClllenpowdery fungus and maintained in the green- PhthtS are utilize; as the t Plant when the house until the mycelial growth appears on the leaf leaves are Y- y are Inoculated Wlth a Water Suspeh' surface. Effectiveness is recorded as the minimum con- Stoh of Spores of h early bhght fungus (/ftltemaris centration, in ppm per lb. of soil, which will provide 50mm. Elhs and M and Placed m an ehvltohmeht 50% reduction in mycelial growth on the leaf surface in of [00% humidity for 48 hours. The plants are then compan'son to untreated, inoculated planm TABLE II Compound Foliar Spray Tube Systemic Soil Drench No. Rust Mildew Tomato Blight Rust Mildew Rust Mildew 1 |000 50 1000 l 6 2 1000 50 1000 0.13 55 6 3 I000 5 0.25 55 6 4 1 000 1000 l 55 5 1000 100 |000 1 55 6 I000 100 5 55 TABLE lI-continued Com pound Foliar Spray Tube System10 Soil Drench No. Rust Mildew Tomato Blight Rust Mildew Rust Mildew BIOCIDE TESTING PROCEDURES TABLE "Lcominued Tubes of sterilized nutrient and malt extract broth Compound are prepared. Aliquots of the toxicant, dissolved in an No. A.n. P.i. E.c. $.11. appropriate solvent, are injected through the stopper, 35 23 50 5 50 50 mto the broth, to provide concentrations ranging from 24 50 50 50 50 50 ppm downward. The test organisms consist of two g2 I Z fungi, Aspergillus niger (A.n.) van Tieghem and Penicil- 27 1 50 .50 lium italicum (P.i.) Wehmer, and two bacteria, Esclzerif; iclzia coli (E.c.) Migula and Staphylococcus Ltureus 40 3 50 50 50 4 (S.a.) Rosenbach. Three drops of a spore suspension of 31 50 50 50 25 each of the fungi are injected into the tubes of malt g broth and three drops of the bacteria are injected into 34 50 50 50 50 the nutrient broth. One week later the growth of each 32 organism is observed and effectiveness of the chemical 37 25 is recorded as the lowest concentration in ppm which 38 50 25 provides 50% inhibition of growth as compared to un- Pam, comm, treated inoculated tubes. The results of these tests are tab d Tabl III.

late m e The compounds of thlS Invention are generally em- TABLE III 50 bodied into a form suitable for convenient application. Compound For example, the compounds can be embodied into No. A.n. P.i. Be. .21. pesticidal composition which are provided in the form 1 (50) (5) 50 50 of emulsions, suspensions, solutions, dusts and aerosol z 50 (1 50 50 sprays. In general, such compositions will contain, in i :28 :28 g8; addition to the active compound, the adjuvants which 5 50 (5) 50 50 are found normally in pesticide preparations. In these 3 i8 Z28 gg compositions, the active compounds of this invention 8 50 (50) 50 50 can be employed as the sole pesticide component or 9 50 (50) 28 Z 8 they can be used in admixture with other compounds 1? :28 T Z 2 having similar utility. The pesticide compositions of 12 50 (25) 50 50 this invention can contain, as ad'uvants, or anic sol- J g :2 :28 32 28 vents, such as sesame Qll, xylene range solvents, heavy 1 50 50 50 50 etroleum, etc.; water; emulsif in a ents; surface ac- 5 v I I g 16 50 50 50 t1ve agents; talc; pyrophylhte; dlatomite; gypsum; clays; 17 50 50 50 50 I 50 50 50 50 propellants, such as dlchlorodlfluoromethane. etc. If 19 50 50 50 50 desired, however, the active compounds can be applied 3? directly to feedstuffs, seeds, etc, upon which the pests 22 50 50 50 50 feed. When applied in such a manner, it will be advan- 7 8 tageous to use a compound which is not volatile. ln 7. A method as set forth in claim 1 wherein R is connection with the activity of the presently disclosed pesticidal compounds, it should be fully understood that it is not necessary that they be active as such. The -Cl purposes of this invention will be fully served if the compound is rendered active by external influences, and RI is SUCh as light or y some physiological action which 8. A method as set forth in claim 1 wherein R is occurs when the compound is ingested into the body of the pest.

The precise manner in which the pesticidal composil tions of this invention are used in any particular instance will be readily apparent to a person skilled in the and R1 is OCH2CH3 art. Generally, the active pesticide compound will be 9 A method as Set forth in Claim 1 wherein R is embpdied in thelform of a liquid composition;l for ex- E and R1 is amp e. an emu sion. suspension, or aeroso spray. While the concentration of the active pesticide in the g Set 5% 3 1 wherein R 15 present compositions can vary within rather wide lim- 2 3 an 2 its, ordinarily the pesticide compound will comprise not more than about 15.0% by weight of the composition. Preferably, however, the pesticide compositions CH of this invention will be in the form of solutions or 3 suspensions containing about 0.1 to 1.0% by weight of the active pesticide compound.

What is claimed is:

l. A method of controlling pests selected from the group consisting of fungi and bacteria consisting of adding to the habitat thereof a fungicidally and bactericidally effective amount of a compound having the 11. A method as set forth in claim 1 wherein is and R1 iS -'OCH3.

12. A method as set forth in claim 1 wherein R is generic formula: and R is OCH CH CH 13. A method as set forth in claim 1 wherein R is -SO R and R1 iS OCH3.

2 14. A method as set forth in claim 1 wherein R is fi fi 1 and R1 iS s 15. A method as set forth in claim 1 wherein R is CH CH CH and R is OCH CH CH 16. A method as set forth in claim 1 wherein R is wherein R can be selected from lower alkyl, lower and R1 i 0 haloalkyl, phenyl, substituted phenyl wherein said sub- 7 A method as set f h in Claim 1 wherein R is stituents can be selected from halogen and lower alkyl;

R can be selected from lower alkoxy and lower thioal- 4O 2. A method as set forth in claim 1 wherein R is and R is OCH CH CH 3 18. A method as set forth in claim 1 wherein R is and R, is ocn cn 3. A method as set forth in claim 1 wherein R is CH3 and R1 iS and R1 is O(:H2CH2CH3.

4. A method as set forth in claim 1 wherein R is 19- A method as set forth in claim 1 wherein R is CH and R is OCH CH CH and R is SCH CH 5. A method as set forth in claim 1 wherein R is 20. A'method as set forth in claim 1 wherein R is CH,, and R is O-(-CH CH 21. A method as set forth in claim I wherein R is 0 CH and and R is ocn CH.-,

6. A method as set forth in claim 1 wherein R is 22. A method as set forth in claim 1 wherein R is Q and R is OCH CH and R is SCH CH 23. A method as set forth in claim 1 wherein R is and R is 26. A method as set forth in claim 1 wherein R is (-CH CH and R, is OCH CH CH;. 27. A method as set forth in claim 1 wherein R is OCH\ and R1 iS 28. A method as set forth in claim I wherein R is -CH Cl and R is OCH CH 24. A method as set forth in claim 1 wherein R is 29- A method as set forth in Claim 1 wherein R is and R is O(-CH CH 25. A method as set forth in claim 1 wherein R is and R is OCH CH- and R is UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,927,219 DATED December 16, 1975 INVENT0R(5) I Alexander Mihailovski It is certified that error appears in the ab0ve-identified patent and that said Letters Patent are hereby corrected as shown below: 0

In Column 8, Claim 21 (Claim 69 in the original appkicationy after "and" and before CH -OCH cH please insert R is" Signed and Scaled this 0 Fifteenth Day Of February 1977 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner oflarenrs and Trademarks 

1. A METHOD OF CONTROLLING PESTS SELECTED FROM THE GROUP CONSISTING OF FUNGI AND BACTERIA CONSISTING OF ADDING TO THE HABITAT THEREOF A FUNGICIDALLY AND BACTERICIDALLY EFFECTIVE AMOUNT OF A COMPOUND HAVING THE GENERIC FORMULA:
 2. A method as set forth in claim 1 wherein R is
 3. A method as set forth in claim 1 wherein R is -CH3 and R1 is -OCH3.
 4. A method as set forth in claim 1 wherein R is -CH3 and R1 is -OCH2CH3.
 5. A method as set forth in claim 1 wherein R is
 6. A method as set forth in claim 1 wherein R is
 7. A method as set forth in claim 1 wherein R is
 8. A method as set forth in claim 1 wherein R is
 9. A method as set forth in claim 1 wherein R is -CH2CH3 and R1 is -OCH3.
 10. A method as set forth in claim 1 wherein R is -CH2CH3 and R1 is -OCH2CH3.
 11. A method as set forth in claim 1 wherein R is
 12. A method as set forth in claim 1 wherein R is
 13. A method as set forth in claim 1 wherein R is -CH2CH2CH3 and R1 is -OCH3.
 14. A method as set forth in claim 1 wherein R is -CH2CH2CH3 and R1 is -OCH2CH3.
 15. A method as set forth in claim 1 wherein R is -CH2CH2CH3 and R1 is -OCH2CH2CH3.
 16. A method as set forth in claim 1 wherein R is -CH3 and R1 is -OCH2CH2CH3.
 17. A method as set forth in claim 1 wherein R is
 18. A method as set forth in claim 1 wherein R is
 19. A method as set forth in claim 1 wherein R is -CH3 and R1 is -SCH2CH3.
 20. A method as set forth in claim 1 wherein R is -CH3 and R1 is -O-CH2)3 CH3.
 21. A method as set forth in claim 1 wherein R is -CH3 and
 22. A method as set forth in claim 1 wherein R is
 23. A method as set forth in claim 1 wherein R is
 24. A method as set forth in claim 1 wherein R is
 25. A method as set forth in claim 1 wherein R is
 26. A method as set forth in claim 1 wherein R is -CH2)3 CH3 and R1 is -OCH2CH3.
 27. A method as set forth in claim 1 wherein R is -CH2)3 CH3 and R1 is -OCH2CH2CH3.
 28. A method as set forth in claim 1 wherein R is -CH2Cl and R1 is -OCH2CH3.
 29. A method as set forth in claim 1 wherein R is 